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Stereoconvergent preparation of chiral vinylsilanes by cuprate substitution of α-acetoxyallylsilanes. Application to the synthesis of ( S )-(+)-bishomomanicone


Guintchin, Boris; Bienz, Stefan (2003). Stereoconvergent preparation of chiral vinylsilanes by cuprate substitution of α-acetoxyallylsilanes. Application to the synthesis of ( S )-(+)-bishomomanicone. Tetrahedron, 59(38):7527-7533.

Abstract

Enantiomerically enriched (E)- and (Z)-configured a-acetoxyallylsilanes have been prepared starting from a chiral acylsilane bearing an asymmetric unit at the silicon portion. Treatment of these compounds with organocuprates afforded the respective vinylogous substitution products in high yields and high stereoselectivities. The transformations proceed essentially by complete anti attack of the nucleophiles to the allylic acetates and predominantly via transition states leading to the (E)-configured vinylsilane products. By the proper
choice of the double bond geometry in the starting material, the configuration of the newly formed stereogenic center can be controlled. The method represents a new and flexible entry into chiral vinylsilanes that can be used for subsequent transformations. As an example, the a,b-unsaturated g-chiral, naturally occurring ketone (S)-(þ)-bishomomanicone was synthesized with this method, which represents the first synthetic access to this compound.

Abstract

Enantiomerically enriched (E)- and (Z)-configured a-acetoxyallylsilanes have been prepared starting from a chiral acylsilane bearing an asymmetric unit at the silicon portion. Treatment of these compounds with organocuprates afforded the respective vinylogous substitution products in high yields and high stereoselectivities. The transformations proceed essentially by complete anti attack of the nucleophiles to the allylic acetates and predominantly via transition states leading to the (E)-configured vinylsilane products. By the proper
choice of the double bond geometry in the starting material, the configuration of the newly formed stereogenic center can be controlled. The method represents a new and flexible entry into chiral vinylsilanes that can be used for subsequent transformations. As an example, the a,b-unsaturated g-chiral, naturally occurring ketone (S)-(þ)-bishomomanicone was synthesized with this method, which represents the first synthetic access to this compound.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:stereoconvergent, chiral vinylsilanes, α-acetoxyallylsilanes, (S)-(+)-bishomomanicone
Language:English
Date:September 2003
Deposited On:23 Aug 2017 16:12
Last Modified:09 Dec 2017 01:52
Publisher:Elsevier
ISSN:0040-4020
Publisher DOI:https://doi.org/10.1016/S0040-4020(03)01169-4

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